Sulphonates of polyaryl polyethers



Patented Aug. 2s, 193s 3,111,493 1 smnomrrss or ronnan. roaramas Berman ABl-uson,

Pa., assilnor to Philadelphia, Bhm ls Baas Company, Philadelphia. Pa.

No Drawing'. Application April 8. 1931, Serin! N0. 135.671

14 Claim (in. 20D-511) nuclear chloro, alkoxy, or sulphonic and derivatives of the above phenolic compounds. The alkyl or acyl groups can be branched-chainfor straight-chain in character. Fior practical reasons the alkyl phenols having from four to 5 eighteen carbon atoms in the alkyl group are This invention relates to new capillary active compounds; namely. sulphonatcs and polysulphonates o! aromatic polyethers having the gen- A eral formula lt'-0A-DR wherein R and 6 Il.' are each aromatic nuclei. "at least one of `which contains a nuclear hydrocarbon or acyl substituent having more than three carbon atoms. and A is an aliphatic group, preferably an alkylene group or a poiyalkylene ethergroup in l which at least two carbon atoms separate successive 'ether atoms.

These products are useful as wetting, emulsii lying, cleansing and spreading agent-5,. and as introiying agents in the textile industry.

In general, they are prepared in two or more stages, irom a phenol having a nuclear hydrocarbon or acyl substituent of more than three carbon atoms. an aliphatic compound containing a halogen atom on two oi its terminal carbon zo atoms, and a sulphonating agent. Among the various 'alternative speciilc procedures that can be used may be mentioned the following- 1. Two mois of the phenol can be condensed with one mol oi' the aliphatic dihalide in the presas ence oi'lcaustic alkali to form the diary] diether which can then `be sulphonated.

2. Two mois oi.' a sulphonated phenol of the class described can becondensed with one mol oi' the aliphatic dihalide in the presence oi caus- 80 ,tic alkali. 4

3. One mol of the phenol can be condensed with one mol of the aliphatic dihalide. in the presence of caustic alkali so. as to etheriiy only one end of the dihalide and the resulting product s6 ci'mdcnsed with the same or a different phenol in the presence ot caustic alkali to etherily the other end. The product may then be suiphonated or one of the starting phenol. or both, may be -sulphonated prior to condensation.

4. Two mois of aryloxy aliphatic halide obtained by the reaction fo! one mol of a phenol and one'oi aliphatic dihalide, as above. can be reacted with sodium sulphide as described in detail in my copatent application Serial No. 117,510

44.6 'med December 24. 1936. and the product sulphonated. out two' halide used in place ot the sodium sulphide.

These reactions are applicable to such phenols 60 'as butyl. amyl, hexyl. cyclohexyl. benzyl, phenyl.

'octyl, decyl, undecy.. lauryl, oleyl. cetyl. or ocgtadecylphenols or the corresponding cresols. xylenols or naphthols; the butyryl. valeryl, octoyl, dodecoyl.: stearoylphehnl. the correspond- Other compounds capable of splitting ci ing cresols. xylenols. or naphthols. as Well as. the

atomsinasimilarwaycanbe i for 3 hours.

preferred.

It is not necessary that both the aromatic groups be derived imm substituted phenols. Il'

one contains a tour or more carbon atom hydro carbon or acyl group. the-other may be unsubstituted or contain a substituent of less than four carbon atoms.

As examples of the aliphatic use ethylene dichloride, propyiene dichlorlde,

dihalides, one can diisopropyl ethyl ether, or the corresponding thloethers. y

morder to illustrate the invention the following examples are given with the understanding that the-invention is not restricted to them.

Example 1.-Bis- (il-ter-octylphenoxy) -ethanedisulphonate. A mixture consisting o! 412 g. psa,-

amv-tetramethylbutylphenol (U. B. Patent 2,008,011) 09 g. ethylene dichloride. 400 cc. water.

and 93.6 g, sodium hydroxide iron autoclave with constant agitation for 6 hours C. The product obtained was boiled at o-100 was heated in an with water. 'I he oil layer, after cooling. solidified to a crystalline mass of hisp(p,,y,ytet ramethylbutylphenoxy) -etnane which 'from alcohol in colorless crystals melting at 81-83 C'. Yield 405 g. This product was disulphonated by dissolving 87.8 g. in 250 g. of ethylene dlchloride and cooling the solution to `0 C., s. of chlorsulphonic acid with during which time the temperature rose to 15 added. the temperature C. After all had been then adding dropw'ise 49 constant stirring.

was allowed to rise to -30 C. and held thereat heating at sodium hydroxide to dryness. a white is'soluble in hot a very low interfacial allll'roihandisusefulasan The reaction was completed by C. for i hours. was then added and the mixture neutralized with solution. Upon evaporating powder was obtained which water to sive a solution having tension when measured 350 cc. oi' water emulsifrlns arent. ss

96 g. of the above compound was dissolved in 300 g. ethylene dichloride. To this solution, with stirring and cooling to 10 C., 49 g. chlorsulphonic acid was added dropwise during 45 minutes. After stirring for an additional 3 hours at room temperature, the solvent was evaporated ofi under reduced pressure on a water bath. The crude product obtained was recrystaliized from hot water. It is the free disulphonic acid and forms iine. colorless needles. The sodium and potassium salts are soluble in hot water to give a very foamy solution. The triethanolamine salt is soluble in cold water and is useful as a wetting agent. p

Example 3.-A mixture consisting of 206 g. p-mafyfytetramethylbutylphenol, 94 g. -chlorethoxy-'chlorodiethyl ether, 46.8 g. sodium hydroxide, and 200 cc. water was heated in an iron autoclave for 6 hours with good agitation at 170- 180 C. I'he product was washed with hot water, leaving Van oil which rapidly crystallized. It forms colorless crystals, M. P. 'l2-'73 C. (from alcohol). Yield 256 g.' The product has the formula- ClHi'r-CcHl-O-CHa-CHa-O- CHz-CHa-O-CHa-CHa-O-CHl-CBHW A solution of 105 g. of the above product in 300 g. ethylene dichloride was reacted at room temperature with 49 g. chlorsulphonic acid added dropwise with constant stirring. The temperature rose to 40 C. The mixture was stirred for 2 hours and allowed to stand 3 hours. 200 cc. of water was then added and the free disulphonlc acid was neutralized with sodium hydroxide solution. The solvent and water were removed by evaporation under reduced pressure, leaving a white powder which was readily soluble in cold water to give a solution having powerful capillary activity.

Example 4,-A mixture consisting of 300 g. p-ter-butyl-phenol. 99 g. ethylene dichlorlde, 400 cc. water, and 93.6 g. sodium hydroxide was heated in an iron autoclave with stirring for 6 hours at 180-1901 C. The crystalline product obtained was purified by crystallization from alcohol. It has thue formulaand melted at 91 C.

A solution of 65.2 g. oi the above ether in 200 g. ethylene dichloride was cooled to 10 C. and with agitation and cooling, 49 g. chlorsulphonic acid was added dropwise during one hour. The

mixture was stirred for 3 hours thereafter at tained was a white powder, which dissolved in water to a foamy solution having good wetting properties.

Example 5.-A mixture consisting `of 103 g. pa.a,q,y-tetramethylbutyl phenol. 100 g. -phenoigy'chlorodiethyl ether, 23 g. sodium hydroxide, and 200 cc. water was heated with stirring in an iron autoclave for 6 hours at 1GO-190 C. The oil obtained was washed thoroughly with water. It crystallized in the cold to a waxy mass. After recrystallization from alcohol, a product melting at 53-54 C. and having the formula Ginn-Occurs nro-o Broni-o@ was obtained.

To a solution of 74 g. of the above ether in 200 g. ethylene dichlori e, there was added, between and 30 C., with agitation, 49 g. oi chlorsuiphonic acid. The mixture was stirred for 18 hours at room temperature, and then neutralized with 10% sodium hydroxide solution. The water and solvent were then evaporated od under reduced pressure. leaving the white powdery disulphonate, useful as a wetting agent.

Example 6,-A mixture consisting of 31.3 g.

-p-a,u,y,ytetramethylbutylphienoxy-n chloro.- diethyl ether, 20 g. p-phenol-sodium sulphonate, 4.3 g. sodium hydroxide, and 150 cc. oi water was heated at 18o-190 C. with stirring in an autoclave for 6 hours. The soap-like product obtained consists of the p-ter-octylphenoxyethoxyethyl ether of phenol-sodium sulphonate, having the formula CIHfO-o-onrcnro-onronro-Os oiNa Example 7.--A mixture of 300 g. p-ter-butylphenol, 92.6 g. sodium hydroxide, 400 g. water, and 143 g. ,'-dlchlorodiethyl ether was heated, with stirring, in an autoclave for 6 hours at 180- 190 C. The oil was washed with water and crystallized from alcohol. The product is C4He--CcI-I4-O--CHa-CH2- O-CHa-CHn-O--CoHe-ClHe It forms colorless crystals, M. P. 3435 C.

76 g. of the above crystals dissolved in 200 g. ethylene dihloride was sulphonated as in Example 4 with 49 g. chlorsulfonic acid. 'I'he disulfonic acid formed was neutralized with potassium hydroxide solution and the solution evaporated to dryness. The dlsuiphonate is a watersoluble white powder which gives a foamy solution. vIt is useful as an introfying agent.

Example 8.A mixture consisting of 72 g. naphthol, 23.4 g. sodium hydroxide. 600 cc. water and 156 g. of -(p-,a.yn-tetramethylbutylphenoxy) -p-chlorodiethyl ether was heated at 180- 190 C. for 6 hours, with stirring, in a steel autoclave. The productY obtained was a low melting waxy mass, having the formula CcHiv-CcHl-O-Cla-CHr- O-CHa-CHn--O-CwHr To a solution of 84 g. oi' the ,above -ter-octylphenoxy-p'naphthoxydiethyl ether in 200 g. ethylenedlchloride, there was added, while stirring and cooling, 73.4 g. oi chlorsulphonic acid. After stirring for 6 hours at room temperature, the disulphonic acid formed was neutralized with aqueous sodium hydroxide solution and evaporated to dryness. The product was a creamy 9,171,498 colored water-soluble powder, capable of lowering.

the surface tension of water toa marked degree.

Example, 9.-A mixture consisting oi 300 g. pter-butyiphenol, 187 g. pchloroethoxy-p'chloro diethyl ether, 94 g. lsodium hydroxide, and 400 cc. of water was heated at 180-190" C. for 6 hours. with stirring, in a steel autoclave. The oil formed consisted essentially of the compound It formed colorless crystals, M. P. 32 C. (from alcohol).

To a solution of 82 g. of the above pter-butyl phenoxy-ethoxy p-ter-butyiphenoxy diethyl ether in 200 g. ethylene dichloride, there was added 45 g. of luming suiphuric acid (20% S03) at 0--5o C. and the mixture stirred for 8 hours thereafter at 20-25" C. The product obtained cmu-Owom-Onr-o-cnlom-o@ came over at 23o-250 0./4 mm. as a pale yellow oil.

37 g. oi' the above oil in l00g. ethyl acetate was sulphonated at 10-20" C. with 24 g. chlorulphonio acid and neutralized with 10% caustic soda solution. The foamy solution obtained, iupon evaporation, gave a white powder useful as a wetting agent. f

Example 14.-2'Irisulphonate of cmu-Oo-cnr-onro-csworn-00CHF@ c. with 1an g. chxorsmpnonic acid for nve hours.

The solution was neutralized with a 10% sodium hydroxide solution and evaporated to dryness in vacuo. The product was a white powder useful as an emulsiiying agent.

Example 11.--The condensation product of laurylphenol and chloroethoxy'chlorodiethyi ether having the probable formula cnHw-cm-o-crn-cmo-CHz-cHi-o-cmcmcl was heated with a molecular equivalent quantity of phenol and sodium hydroxide, together with an equal'volume of water at 190 C. for 14 hours in an autoclave, with stirring. The product was an oil which, upon sulphonation with4 2 mol equivalents of chlorsulphonic acid. gave a very foamy, soapy disuiphonic acid. The ammonium or sodium salt thereof can be used as a detergent. Example 12.-Disulphonate of clm-Oomnrcm-o-c Bro HroO-om ter-octylphenoxy-diethyl ether was dissolved in g. of ethylene dichloride and sulphonated at 5-10" C. with24.3 g. chlorsulphonic acid. The product was neutralized with sodium hydroxide solution and evaporated to dryness in vacua, leaving a white water-soluble powder, useful as a wetting agent.

A mixture consisting of 156 g. (ia-manqtetramethylbutylphenoxy) chlor'odiethyl ether, 92 g.- p-benzylphenol, 23.4 g. sodium hydroxide, and 400 g. water', was heated i8 hours in'a steel autoclave at 18o-190 C., with stirring. The product was washed with hot water. YOn cooling. the

oil layer 'solidified to a waxy crystalline mass.

The pure p(p-a,amfp-tetramethyibutylphenoxy-t (pbenzylphenoxy)diethyl ether crystiliimes from methanol in colorless crystals, M. P. $4" C. Yield 230 g. 4

A solution of 46 g. oi' the above product in i g. ethylene dichioride was sulphonated at 20 C. with 36.5 g. chiorsulphonic acid for 6 hours. The solution was then neutralized with 10% sodiumA hydroxide solution and evaporated to dryness in vacuo. The product was a white water-soluble powder useful as a penetrant.

Example 15.-A mixture consisting of 10B g. -p-s, a. 1, 'y-tetramethylbutylphenoxy-p'-chlorodlethyi ether, 65 g. sodium sulphide (Nass- 60% purity) and 200 g. alcohol was boiled under reilux, with stirring, for 12 hours; The solution was filtered, the alcohol evaporated ofi'. the residual oil taken up in benzene. illtered free from inorganic salts, washed with water, dried, and the' benzene removed by evaporation. The product was a paie yellow. viscous oil, having the formula A solution oi 29 g. oi the above thioether in 50 g. ethylene dichloride was sulphonated at 1015 C. with 12.2 g. .chlorsulphonic acidl'or 6 hours. The product was then neutralized with 10% sodium hydroxide solution and evaporated to dryness. The product obtained was a watersoluble, soap-like mass.

Example 16.-A mixture consisting oi' 00.8 g. p-ter-butyl-phenol, '94 g. 1.10-dicl'ilor-decane, 20.8 g. sodium hydroxide. and 400 cc. water. 'was heated, with stirring, in an autoclave. for 8 hours at 18o-190 C. The crystalline product obtained, namely, 1,10-di-p-ter-butylphenoxy-decane, after crystallization from alcohol, formed colorless crystals, M. P. 50 C. Upon sulphonation with 2 mol equivalents of chlorsulphonic acid and neu' tralizatlon with potassium hydroxide, a. disulphonate was obtained which is soluble in hot water to give a i'oamy solution.

In the above examples the alkyl phenols used may be replaced mol for mol by any other alkyl 0r acylphenol or naphthol having at least 4 carbon atoms in the alkyl or acyl group to yield similar products.

I claim:

l. A sulphonate of an aromatic polyether having the general formula R-O-A-O-R in which R and R' are each aromatic groups at least one o1' which contains a nuclear substituent of the group consisting of hydrocarbon and acylV groups of more than three carbon atoms and A is a member of the group consisting of alkylene groups and poiyalkylene ether groups in which at least two carbon atoms separate successive ether atoms.

2. A sulphonate of an aromatic polyether having the general formula R-O-A-O-R' in which R and R' are aromatic groups at least one of which contains an alkyl substituent oi' more than three carbon atoms and A is a member of the group consisting of alkylene groups and polyalkylene ether groups in which at least two carbon atoms separate successive ether atoms.

3. A sulphonate of an aromatic polyether having the general formula R-O-A-O-R' in which R. and R are aromatic groups of the benzene series at least one of which contains an alkyl substituent of more than three carbon atoms and A is a polyallwlene ether group in which at least two carbon atoms separate successive ether atoms.

4. A sulphonate oi an aromatic polyether havlng the general formula Rf-O-A-O-R' in which R. and R.' are aromatic groups of the benzene series at least one oi which contains an acyl substituent oi' more than three carbon atoms and A is a polyalkylene ether group in which at least two carbon atoms separate successive ether atoms.

5. A sulphonate oi' an aromatic polyether having the general formula in which Z is an alkyl group having from 4 through 18 carbon atoms and R' is an aromatic nucleus.

Patent No. 2,17l,l|.98.

6. A sulphonate of an aromatic polyether having the Eeneral formula in which Z is an alkyl group having from 4 through 18 carbon atoms and R' is an aromatic nucleus of the benzene series.

'1. A disulphonate of bis-'(pa,a,'y,'ytetramethylbutyl phenoxy) diethyl ether.

8. A process which`comprises reacting in a plurality of stages two molecular equivalents of a phenol containing a nuclear substituent of the group consisting of hydrocarbon and acyl groups ci more than three carbon atoms with one molecular equivalent of an aliphatic dihaiide in which the halogen atoms are on two terminal carbon atoms, and a sulphonating agent.

9. A process which comprises reacting in a plurality of stages two molecular equivalents of a phenol containing an alkyl substituent of more than three carbon atoms with one molecular equivalent ci' a member of the group consisting oi' alkylene dihalides and polyalkylene ether dihalides in which the alkylene groups contain at least two carbon atoms, and a sulphonating agent.

10. A process which comprises reacting in a plurality ot stages two molecular equivalents of a phenol containing an alkyl substituent of at least three carbon atoms with one molecular equivalent of a polyethylene dihalide and a sulphonating agent.

l1. A process which comprises reacting in a plurality of stages a.a,-y.7tetramethylbutyl phenol with one molecular equivalent of dichlor diethyl ether, and a sulphonating agent.

12. A process oi' producing the compounds claimed in claim 1 which comprises reacting in a plurality of stages a sulfonating agent, one molecular equivalent each of phenols having the formula ROH and R'OH and one molecular equivalent ci' an aliphatic dihalide -of the formula X-A-X, wherein R, R', and A have the values speciiecl in claim 1 and X represents halogen atoms attached to terminal carbon atoms of A.

13. A water-soluble sulphonate of -laurylphenoxy-phen0xyethoxydietlwl ether.

14. A water-soluble sulphonate of -p-ter-butylphenoxy-ethoxy-p'-p-ter-butylphenoxy diethyl ether.

HERMAN A. BRUSON.

CERTIFICATE or CORRECTION.

August 29, 1959 HERrmN A. BRUsoN. g It is hereby certified that error appears :inl the printed specification of the above numbered patent requiring correction asfollows: Page l, sec- :ma column, line 1, rer- "fane" reaeacid; and that the sam Letters Patent should beraad with this correction therein that the same may conform to the record o'f the casein'the Patent Office.

Signed and sealed thisl 10th day` of october, A. D. 1959.

(Seal) Henry van Arsdale, Acting Commissioner of Patents.

phonate was obtained which is soluble in hot water to give a i'oamy solution.

In the above examples the alkyl phenols used may be replaced mol for mol by any other alkyl 0r acylphenol or naphthol having at least 4 carbon atoms in the alkyl or acyl group to yield similar products.

I claim:

l. A sulphonate of an aromatic polyether having the general formula R-O-A-O-R in which R and R' are each aromatic groups at least one o1' which contains a nuclear substituent of the group consisting of hydrocarbon and acylV groups of more than three carbon atoms and A is a member of the group consisting of alkylene groups and poiyalkylene ether groups in which at least two carbon atoms separate successive ether atoms.

2. A sulphonate of an aromatic polyether having the general formula R-O-A-O-R' in which R and R' are aromatic groups at least one of which contains an alkyl substituent oi' more than three carbon atoms and A is a member of the group consisting of alkylene groups and polyalkylene ether groups in which at least two carbon atoms separate successive ether atoms.

3. A sulphonate of an aromatic polyether having the general formula R-O-A-O-R' in which R. and R are aromatic groups of the benzene series at least one of which contains an alkyl substituent of more than three carbon atoms and A is a polyallwlene ether group in which at least two carbon atoms separate successive ether atoms.

4. A sulphonate oi an aromatic polyether havlng the general formula Rf-O-A-O-R' in which R. and R.' are aromatic groups of the benzene series at least one oi which contains an acyl substituent oi' more than three carbon atoms and A is a polyalkylene ether group in which at least two carbon atoms separate successive ether atoms.

5. A sulphonate oi' an aromatic polyether having the general formula in which Z is an alkyl group having from 4 through 18 carbon atoms and R' is an aromatic nucleus.

Patent No. 2,17l,l|.98.

6. A sulphonate of an aromatic polyether having the Eeneral formula in which Z is an alkyl group having from 4 through 18 carbon atoms and R' is an aromatic nucleus of the benzene series.

'1. A disulphonate of bis-'(pa,a,'y,'ytetramethylbutyl phenoxy) diethyl ether.

8. A process which`comprises reacting in a plurality of stages two molecular equivalents of a phenol containing a nuclear substituent of the group consisting of hydrocarbon and acyl groups ci more than three carbon atoms with one molecular equivalent of an aliphatic dihaiide in which the halogen atoms are on two terminal carbon atoms, and a sulphonating agent.

9. A process which comprises reacting in a plurality of stages two molecular equivalents of a phenol containing an alkyl substituent of more than three carbon atoms with one molecular equivalent ci' a member of the group consisting oi' alkylene dihalides and polyalkylene ether dihalides in which the alkylene groups contain at least two carbon atoms, and a sulphonating agent.

10. A process which comprises reacting in a plurality ot stages two molecular equivalents of a phenol containing an alkyl substituent of at least three carbon atoms with one molecular equivalent of a polyethylene dihalide and a sulphonating agent.

l1. A process which comprises reacting in a plurality of stages a.a,-y.7tetramethylbutyl phenol with one molecular equivalent of dichlor diethyl ether, and a sulphonating agent.

12. A process oi' producing the compounds claimed in claim 1 which comprises reacting in a plurality of stages a sulfonating agent, one molecular equivalent each of phenols having the formula ROH and R'OH and one molecular equivalent ci' an aliphatic dihalide -of the formula X-A-X, wherein R, R', and A have the values speciiecl in claim 1 and X represents halogen atoms attached to terminal carbon atoms of A.

13. A water-soluble sulphonate of -laurylphenoxy-phen0xyethoxydietlwl ether.

14. A water-soluble sulphonate of -p-ter-butylphenoxy-ethoxy-p'-p-ter-butylphenoxy diethyl ether.

HERMAN A. BRUSON.

CERTIFICATE or CORRECTION.

August 29, 1959 HERrmN A. BRUsoN. g It is hereby certified that error appears :inl the printed specification of the above numbered patent requiring correction asfollows: Page l, sec- :ma column, line 1, rer- "fane" reaeacid; and that the sam Letters Patent should beraad with this correction therein that the same may conform to the record o'f the casein'the Patent Office.

Signed and sealed thisl 10th day` of october, A. D. 1959.

(Seal) Henry van Arsdale, Acting Commissioner of Patents. 

